EP1642329B1 - Process for producing low-k dielectric films - Google Patents

Process for producing low-k dielectric films Download PDF

Info

Publication number
EP1642329B1
EP1642329B1 EP04741702A EP04741702A EP1642329B1 EP 1642329 B1 EP1642329 B1 EP 1642329B1 EP 04741702 A EP04741702 A EP 04741702A EP 04741702 A EP04741702 A EP 04741702A EP 1642329 B1 EP1642329 B1 EP 1642329B1
Authority
EP
European Patent Office
Prior art keywords
sub
low
dielectric films
polyhedral oligomeric
type
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP04741702A
Other languages
German (de)
French (fr)
Other versions
EP1642329A1 (en
Inventor
Adolf KÜHNLE
Carsten Jost
Hartwig Rauleder
Corne Rentrop
Roelant Van Dam
Klaas Timmer
Hartmut Fischer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP1642329A1 publication Critical patent/EP1642329A1/en
Application granted granted Critical
Publication of EP1642329B1 publication Critical patent/EP1642329B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31695—Deposition of porous oxides or porous glassy oxides or oxide based porous glass

Definitions

  • the invention relates to a process for producing low-k dielectric films on semiconductors for electrical circuits, and to the low-k dielectric films produced by said process.
  • dielectric films having a k value of less than 3.0, referred to as low-k dielectric films.
  • the k value is a measure of the electrical permittivity of a material.
  • Dielectric films are used for insulating the metallic conductors and contribute to the RC time delay and hence to increasing the speed in signal transmission.
  • the RC time delay is a measure of the extent of signal propagation in the conductor tracks, which is slowed by the environment of the conductor tracks, as a result for example of interaction with adjacent conductor tracks; this is referred to as crosstalk.
  • crosstalk The poorer the insulating layer, the greater the unwanted crosstalk.
  • the low-k dielectric films must have further properties in order to be useful as a component for chip fabrication.
  • the low-k dielectric films must exhibit only low thermal expansion at elevated temperature. They ought additionally exhibit effective adhesion to metals, metal oxides and/or metal nitrides. In addition they ought to feature high mechanical stability and be suitable for the operations of planarization (CMP) and etching.
  • CMP planarization
  • silicon dioxide (SiO 2 ) has been the material of choice' for producing dielectric films.
  • the SiO 2 films are produced by depositing silane or siloxane precursors in an oxidizing environment by the CVD (chemical vapor deposition) process.
  • the low-k dielectric films obtainable by this means have relatively high k values of more than 4.0.
  • low-k dielectric films having a k value of from 2.6 to 3.5 the semiconductor industry has developed a number of materials, organic, inorganic and hybrid in nature. These low-k dielectric films can be deposited by means of a CVD process or by means of a SOD (spin-on deposition) process. Newer materials for low-k dielectric films, such as fluorosilicate glasses or carbon-doped SiO 2 can be deposited by means of a CVD process. Low-k dielectric films made from polyimides, polyaryl ethers or polysilsesquioxanes (HSQ) can be produced by means of an SOD process.
  • SOD spin-on deposition
  • Patent application US 2002/0192980 describes the use of completely condensed oligomeric silsesquioxanes for producing low-k dielectric films by a CVD process.
  • Functionalized polyhedral oligomeric silsesquioxanes are reacted with a crosslinker to produce a film structure having a k value of 2.6 or less.
  • the crosslinker used is preferably a silane or siloxane.
  • Crosslinking takes place by free-radical polymerization initiated by silyl or peroxy radicals.
  • Lercher et al. (Adv. Mater. 14 (2002), 1369-73 ) describe the preparation of low-k dielectric films by reaction of oligomeric silsesquioxanes or spherosilicates with suitable crosslinking reagents.
  • hydrosilylation was used to react Si-H-substituted, completely condensed cuboid silsesquioxanes or spherosilicates with 1,5-hexadiene.
  • hydrolytic condensation was used to react Si(OEt) 3 -substituted, completely condensed, cuboid silsesquioxanes or spherosilicates with water to form a three-dimensional network.
  • the layers applied by the SOD process have a k value of from 2.1 to 2.7.
  • a similar approach is pursued by patent application EP 1 036 808 , wherein the desired low-k dielectric films are obtained by hydrosilylating Si-H-substituted, cuboid silsesquioxanes with divinyl-terminated coreactants.
  • JP 2001189109 describes the production of low-k dielectric films having a k value of 2.5 from polybenzoxazoles or precursors thereof and functionalized cuboid oligomeric silsesquioxanes.
  • Patent US 6,329,490 describes the use of completely condensed oligomer silsesquioxanes having fluorinated alkyl radicals for producing low-k dielectric films.
  • fluorosilsesquioxane films by a CVD process is described by patent application WO 01/29141 . These films are produced using as precursors mixtures of silsesquioxanes comprising hydrogen and/or fluorine substituents.
  • the present invention has the advantage over the prior art processes that, with incompletely condensed polyhedral oligomeric silsesquioxanes, favorably priced, readily available reagents are employed which distinctly enhance the economics of the production process.
  • the afore-described processes for producing low-k dielectric films in accordance with the art are characterized by the use of expensive polyhedral oligomeric silsesquioxanes, which in the majority of cases are poorly available and must be prepared in complex fashion by way of multistage syntheses.
  • Incomplete condensed silsesquioxanes of structure 1 in contrast, can be prepared in a one-stage synthesis by hydrolytic condensation of the trialkoxysilanes RSi(OR') 3 in very good yields.
  • Simple monosilylation of the compounds of structure 1 produced incompletely condensed polyhedral oligomeric silsesquioxanes of structure 2. Incompletely condensed polyhedral oligomeric silsesquioxanes of structures 1 and 2 are therefore among the readily available, favorably priced representatives of the class of substance of the oligomeric silsesquioxanes.
  • further coreactants capable of hydrolytic condensation such as alkoxysilanes
  • a further advantage of the process of the invention is that through the choice of the incompletely condensed polyhedral oligomeric silsesquioxanes and of the coreactant capable of hydrolytic condensation it is possible to adjust the porosity and hence also k values of the low-k dielectric film. Thermomechanical strength, hardness, moduli, thermal stability and surface roughness are likewise dependent on the precursors used.
  • the process of the invention for producing low-k dielectric films on semiconductors or electrical circuits is distinguished through the use of incompletely condensed polyhedral oligomeric silsesquioxanes of the formula 1 or 2, with
  • the incompletely condensed polyhedral oligomeric silsesquioxanes used in the process of the invention contain a hydrogen atom or an alkyl, cycloalkyl or alkenyl group as type R substituent.
  • the incompletely condensed polyhedral oligomeric silsesquioxanes used comprise as substituent of type R an alkyl group, in particular a methyl, ethyl, propyl, isobutyl, n-octyl or isooctyl or a 2,2,4-trimethylpentyl group.
  • the incompletely condensed polyhedral oligomeric silsesquioxanes used comprise as substituent of type R a phenyl, cyclopentyl or cyclohexyl group.
  • the substituents of type R may all be identical, though it is also possible for the incompletely condensed polyhedral oligomeric silsesquioxanes to comprise different substituents of type R.
  • Suitable solvents preferably include, in addition to water, organic solvents, particularly alcohols, ketones, ethers, alkanes, cycloalkanes, arenes, nitriles, amines, sulfides, esters, carboxylic acids, amides or unsaturated and halogenated hydrocarbons.
  • Particularly suitable solvents are alcohols, with 1-methoxy-2-propanol being of very special suitability.
  • the incompletely condensed polyhedral oligomeric silsesquioxanes are reacted together with coreactants capable of hydrolytic condensation, preferably with alkoxysilanes, more preferably with tetraalkoxysilanes and very preferably with tetraethoxysilane.
  • coreactants capable of hydrolytic condensation preferably with alkoxysilanes, more preferably with tetraalkoxysilanes and very preferably with tetraethoxysilane.
  • the molar ratio of the incompletely condensed polyhedral oligomeric silsesquioxanes to the coreactant capable of hydrolytic condensation is preferably from 1:100 to 100:1, more preferably from 1:10 to 10:1 and very preferably 2:1.
  • the coreactants capable of hydrolytic condensation are prehydrolyzed or part-hydrolyzed prior to the reaction with the incompletely condensed polyhedral oligomeric silsesquioxanes.
  • This prior or partial hydrolysis of the coreactants capable of hydrolytic condensation can take place either in acidic solution or in neutral solution, and takes place preferably in acidic solution.
  • the coreactants capable of hydrolytic condensation are reacted preferably with water.
  • 50% of the molar amount of water required arithmetically for complete hydrolysis of the coreactant capable of hydrolytic condensation is added.
  • a film former preferably a saturated hydrocarbon, more preferably a saturated hydrocarbon having 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, very preferably hexadecane, is added to the incompletely condensed polyhedral oligomeric silsesquioxane.
  • a pore former preferably a saturated hydrocarbon having 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, very preferably hexadecane
  • Deposition of the starting materials on the substrate takes place preferably by means of a wet-chemical coating method, more preferably by means of spin coating, very preferably at room temperature. In one particular embodiment the deposition may also take place by means of dip coating. This is followed preferably by calcining, in particular at from 400 to 500°C.
  • the invention further provides low-k dielectric films produced by the process of the invention.
  • the low-k dielectric films of the invention preferably have a k value - permittivity - of less than or equal to 2.5, more preferably less than or equal to 2.3 and very preferably less than or equal to 2.1, measured at a frequency of 880 kHz.
  • the k value is determined by a method analogous to that of A.R. Blythe, Electrical Properties of Polymers, Cambridge University Press, ISBN 0 521 29825 3.
  • tetraethoxysilane and water are reacted in a molar ratio of 1:2 (50 g of tetraethoxysilane and 8.65 g of water) at a pH of 2, which is set by adding hydrochloric acid.
  • a molar ratio of 1:2 50 g of tetraethoxysilane and 8.65 g of water
  • pH of 2 which is set by adding hydrochloric acid.
  • the reaction mixture is stirred at room temperature for about 1 day until a clear solution has formed.
  • Table 1 Experimental parameters relating to the preparation of the starting material mixture
  • Example Incompletely condensed polyhedral oligomeric silsesquioxane in accordance with structure 2.1 1 with R isobutyl 1.
  • 2.2 2 with R isobutyl 2.
  • 1.) purchased from Sigma-Aldrich 2.
  • Example Starting Substrate material mixture 3.1 2.1 glass 3.2 2.2 glass 3.3 2.2 conductive glass coated with indium tin oxide (ITO), having a surface resistance of 10 ohms
  • the low-k dielectric films prepared in accordance with example 3.1 and 3.2 exhibit good transparency and wetting.
  • the low-k dielectric films produced according to example 3.3 have a thickness of 550 nm.
  • a gold electrode with a layer thickness of 100 to 500 nm is deposited thereon by means of physical vapor deposition.
  • a measurement is then made of the admittance as a function of frequency at room temperature, using a precision LCR meter HP 4284A. At a frequency f of 880 kHz the k value is 2.3.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Formation Of Insulating Films (AREA)
  • Silicon Polymers (AREA)

Abstract

The invention relates to processes for producing low-k dielectric films on semiconductors or electrical circuits, which comprises using incompletely condensed polyhedral oligomeric silsesquioxanes of the formula [(R<SUB>a</SUB>X<SUB>b</SUB>SiO<SUB>1.5</SUB>)<SUB>m</SUB>(R<SUB>c</SUB>Y<SUB>d</SUB>SiO)<SUB>n</SUB>] with: a, b=0-1; c, d=1; m+n>=3; a+b=1; n, m>=1, R=hydrogen atom or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, in each case substituted or unsubstituted, X=an oxy, hydroxyl, alkoxy, carboxyl, silyl, silyloxy, halogen, epoxy, ester, fluoroalkyl, isocyanate, acrylate, methacrylate, nitrile, amino or phosphine group or substituents of type R containing at least one such group of type X, Y=hydroxyl, alkoxy or a substituent of type O-SiZ<SUB>1</SUB>Z<SUB>2</SUB>Z<SUB>3</SUB>, where Z<SUB>1</SUB>, Z<SUB>2 </SUB>and Z<SUB>3 </SUB>are fluoroalkyl, alkoxy, silyloxy, epoxy, ester, acrylate, methacrylate or a nitrile group or substituents of type R and are identical or different, not only the substituents of type R being identical or different but also the substituents of type X and Y in each case being identical or different, and comprising at least one hydroxyl group as substituent of type Y, for producing the film, and to low-k dielectric films produced by this process.

Description

  • The invention relates to a process for producing low-k dielectric films on semiconductors for electrical circuits, and to the low-k dielectric films produced by said process.
  • The progress in semiconductor technology in tandem with increasing miniaturization is leading to an increasing demand for dielectric films having a k value of less than 3.0, referred to as low-k dielectric films. The k value is a measure of the electrical permittivity of a material. Dielectric films are used for insulating the metallic conductors and contribute to the RC time delay and hence to increasing the speed in signal transmission. The RC time delay is a measure of the extent of signal propagation in the conductor tracks, which is slowed by the environment of the conductor tracks, as a result for example of interaction with adjacent conductor tracks; this is referred to as crosstalk. The poorer the insulating layer, the greater the unwanted crosstalk. In addition to lowering the resistance R by going over to copper as conductor material, reducing the capacitance C through the use of insulating layers with low k values is a further means of increasing the performance of the processors. Through the use of low-k dielectric films it is likewise possible to reduce the RC time delay and hence the crosstalk between adjacent conductor tracks.
  • In addition to a low k value, the low-k dielectric films must have further properties in order to be useful as a component for chip fabrication. For instance, the low-k dielectric films must exhibit only low thermal expansion at elevated temperature. They ought additionally exhibit effective adhesion to metals, metal oxides and/or metal nitrides. In addition they ought to feature high mechanical stability and be suitable for the operations of planarization (CMP) and etching.
  • To date, silicon dioxide (SiO2) has been the material of choice' for producing dielectric films. The SiO2 films are produced by depositing silane or siloxane precursors in an oxidizing environment by the CVD (chemical vapor deposition) process. The low-k dielectric films obtainable by this means have relatively high k values of more than 4.0.
  • For low-k dielectric films having a k value of from 2.6 to 3.5 the semiconductor industry has developed a number of materials, organic, inorganic and hybrid in nature. These low-k dielectric films can be deposited by means of a CVD process or by means of a SOD (spin-on deposition) process. Newer materials for low-k dielectric films, such as fluorosilicate glasses or carbon-doped SiO2 can be deposited by means of a CVD process. Low-k dielectric films made from polyimides, polyaryl ethers or polysilsesquioxanes (HSQ) can be produced by means of an SOD process.
  • Patent application US 2002/0192980 describes the use of completely condensed oligomeric silsesquioxanes for producing low-k dielectric films by a CVD process. Functionalized polyhedral oligomeric silsesquioxanes are reacted with a crosslinker to produce a film structure having a k value of 2.6 or less. The crosslinker used is preferably a silane or siloxane. Crosslinking takes place by free-radical polymerization initiated by silyl or peroxy radicals.
  • Lercher et al. (Adv. Mater. 14 (2002), 1369-73) describe the preparation of low-k dielectric films by reaction of oligomeric silsesquioxanes or spherosilicates with suitable crosslinking reagents. In one instance hydrosilylation was used to react Si-H-substituted, completely condensed cuboid silsesquioxanes or spherosilicates with 1,5-hexadiene. In another instance hydrolytic condensation was used to react Si(OEt)3-substituted, completely condensed, cuboid silsesquioxanes or spherosilicates with water to form a three-dimensional network. The layers applied by the SOD process have a k value of from 2.1 to 2.7. A similar approach is pursued by patent application EP 1 036 808 , wherein the desired low-k dielectric films are obtained by hydrosilylating Si-H-substituted, cuboid silsesquioxanes with divinyl-terminated coreactants.
  • JP 2001189109 describes the production of low-k dielectric films having a k value of 2.5 from polybenzoxazoles or precursors thereof and functionalized cuboid oligomeric silsesquioxanes.
  • Patent US 6,329,490 describes the use of completely condensed oligomer silsesquioxanes having fluorinated alkyl radicals for producing low-k dielectric films.
  • The deposition of fluorosilsesquioxane films by a CVD process is described by patent application WO 01/29141 . These films are produced using as precursors mixtures of silsesquioxanes comprising hydrogen and/or fluorine substituents.
  • Use of oligomeric silsesquioxanes of type H8Si8O12 for producing low-k dielectric films is described in patent application EP 0 962 965 .
  • It was an object of the present invention to provide a process for producing low-K dielectric films that allows more favorably priced or more readily available silsesquioxane raw materials to be used than in prior art processes. In particular it was an object to provide a process enabling low-k dielectric films of virtually the same quality to be produced for lower raw materials costs.
  • Surprisingly it has been found that through the use of the readily available, more favorably priced, incompletely condensed polyhedral oligomeric silsesquioxanes it is possible to produce low-k dielectric films which have a k value of less than or equal to 2.5 as measured at a frequency of 880 kHz. The achievement of object was all the more surprising since it was found that in the reaction of the incompletely condensed polyhedral oligomeric silsesquioxanes with alkoxysilanes a three-dimensional structure is formed which following calcination constitutes ideal insulation materials.
  • The present invention accordingly provides a process for producing low-k dielectric film, which comprises using incompletely condensed polyhedral oligomeric silsesquioxanes of structure 1 or 2
    Figure imgb0001
     with
    R = hydrogen atom or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl group, in each case substituted or unsubstituted, the substituents R being identical or different as starting material for producing the film.
  • The present invention has the advantage over the prior art processes that, with incompletely condensed polyhedral oligomeric silsesquioxanes, favorably priced, readily available reagents are employed which distinctly enhance the economics of the production process. The afore-described processes for producing low-k dielectric films in accordance with the art are characterized by the use of expensive polyhedral oligomeric silsesquioxanes, which in the majority of cases are poorly available and must be prepared in complex fashion by way of multistage syntheses. Incomplete condensed silsesquioxanes of structure 1, in contrast, can be prepared in a one-stage synthesis by hydrolytic condensation of the trialkoxysilanes RSi(OR')3 in very good yields. Simple monosilylation of the compounds of structure 1 produced incompletely condensed polyhedral oligomeric silsesquioxanes of structure 2. Incompletely condensed polyhedral oligomeric silsesquioxanes of structures 1 and 2 are therefore among the readily available, favorably priced representatives of the class of substance of the oligomeric silsesquioxanes. By reacting these incompletely condensed polyhedral oligomeric silsesquioxanes with further coreactants capable of hydrolytic condensation (such as alkoxysilanes) it is possible to obtain new kinds of three-dimensional network structures which are suitable directly or following calcination as porous low-k dielectric films.
    Figure imgb0002
  • A further advantage of the process of the invention is that through the choice of the incompletely condensed polyhedral oligomeric silsesquioxanes and of the coreactant capable of hydrolytic condensation it is possible to adjust the porosity and hence also k values of the low-k dielectric film. Thermomechanical strength, hardness, moduli, thermal stability and surface roughness are likewise dependent on the precursors used.
  • The process of the invention for producing low-k dielectric films on semiconductors or electrical circuits is distinguished through the use of incompletely condensed polyhedral oligomeric silsesquioxanes of the formula 1 or 2, with
  • In the process of the invention it is preferred to use incompletely condensed polyhedral oligomeric silsesquioxanes containing not more than three hydroxyl groups as substituents.
  • With particular preference the incompletely condensed polyhedral oligomeric silsesquioxanes used in the process of the invention contain a hydrogen atom or an alkyl, cycloalkyl or alkenyl group as type R substituent. With very particular preference the incompletely condensed polyhedral oligomeric silsesquioxanes used comprise as substituent of type R an alkyl group, in particular a methyl, ethyl, propyl, isobutyl, n-octyl or isooctyl or a 2,2,4-trimethylpentyl group. In one particular embodiment of the process of the invention the incompletely condensed polyhedral oligomeric silsesquioxanes used comprise as substituent of type R a phenyl, cyclopentyl or cyclohexyl group. The substituents of type R may all be identical, though it is also possible for the incompletely condensed polyhedral oligomeric silsesquioxanes to comprise different substituents of type R.
  • In accordance with the process of the invention the incompletely condensed polyhedral oligomeric silsesquioxanes can be used either as the substance per se or in solution. Suitable solvents preferably include, in addition to water, organic solvents, particularly alcohols, ketones, ethers, alkanes, cycloalkanes, arenes, nitriles, amines, sulfides, esters, carboxylic acids, amides or unsaturated and halogenated hydrocarbons. Particularly suitable solvents are alcohols, with 1-methoxy-2-propanol being of very special suitability.
  • In one particular embodiment of the process of the invention the incompletely condensed polyhedral oligomeric silsesquioxanes are reacted together with coreactants capable of hydrolytic condensation, preferably with alkoxysilanes, more preferably with tetraalkoxysilanes and very preferably with tetraethoxysilane. In this reaction the molar ratio of the incompletely condensed polyhedral oligomeric silsesquioxanes to the coreactant capable of hydrolytic condensation is preferably from 1:100 to 100:1, more preferably from 1:10 to 10:1 and very preferably 2:1.
  • In one very special embodiment of the process of the invention the coreactants capable of hydrolytic condensation are prehydrolyzed or part-hydrolyzed prior to the reaction with the incompletely condensed polyhedral oligomeric silsesquioxanes. This prior or partial hydrolysis of the coreactants capable of hydrolytic condensation can take place either in acidic solution or in neutral solution, and takes place preferably in acidic solution. For this purpose the coreactants capable of hydrolytic condensation are reacted preferably with water. In one particular embodiment, for this prior or partial hydrolysis, 50% of the molar amount of water required arithmetically for complete hydrolysis of the coreactant capable of hydrolytic condensation is added.
  • In another embodiment of the process of the invention a film former, preferably a saturated hydrocarbon, more preferably a saturated hydrocarbon having 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms, very preferably hexadecane, is added to the incompletely condensed polyhedral oligomeric silsesquioxane. In one special embodiment of the process of the invention it is also possible to use a pore former.
  • Deposition of the starting materials on the substrate, which may be a semiconductor or a circuit, takes place preferably by means of a wet-chemical coating method, more preferably by means of spin coating, very preferably at room temperature. In one particular embodiment the deposition may also take place by means of dip coating. This is followed preferably by calcining, in particular at from 400 to 500°C.
  • The invention further provides low-k dielectric films produced by the process of the invention. The low-k dielectric films of the invention preferably have a k value - permittivity - of less than or equal to 2.5, more preferably less than or equal to 2.3 and very preferably less than or equal to 2.1, measured at a frequency of 880 kHz. The k value is determined by a method analogous to that of A.R. Blythe, Electrical Properties of Polymers, Cambridge University Press, ISBN 0 521 29825 3.
  • The example which follows is intended to illustrate the process of the invention, without any intention that the invention should be limited to this embodiment.
    • 1. Prehydrolysis of the coreactant capable of hydrolytic condensation
  • For prehydrolysis of tetraethoxysilane, tetraethoxysilane and water are reacted in a molar ratio of 1:2 (50 g of tetraethoxysilane and 8.65 g of water) at a pH of 2, which is set by adding hydrochloric acid. For this reaction the reaction mixture is stirred at room temperature for about 1 day until a clear solution has formed.
    • 2. Preparation of the starting material mixture
  • 20% by weight of an incompletely condensed polyhedral oligomeric silsesquioxane is dissolved in 1-methoxy-2-propanol. Subsequently 10% by weight of hexadecane are added to this solution. In a further step the prehydrolysis product from step 1 is added at room temperature to the solution of the incompletely condensed polyhedral oligomeric silsesquioxane, the molar ratio of tetraethoxysilane to the incompletely condensed polyhedral oligomeric silsesquioxane being 2:1. Table 1: Experimental parameters relating to the preparation of the starting material mixture
    Example Incompletely condensed polyhedral oligomeric silsesquioxane in accordance with structure
    2.1 1 with R = isobutyl1.)
    2.2 2 with R = isobutyl2.)
    1.) purchased from Sigma-Aldrich
    2.) prepared by silylation using trimethylsilyl chloride and the incompletely condensed polyhedral oligomeric silsesquioxane of structure 1.
    • 3. Deposition of the starting material mixture
  • 0.5 ml of each of the starting material mixtures from step 2 is deposited by spin coating on a substrate having a surface area of 6.45 cm2 and rotating at a speed of 1200 rpm over the course of 2 minutes. Subsequently the coated substrates are dried initially at room temperature and then calcined at 450°C in an air atmosphere over the course of 1 hour.
    Example Starting Substrate
    material
    mixture
    3.1 2.1 glass
    3.2 2.2 glass
    3.3 2.2 conductive glass coated with indium tin oxide (ITO), having a surface resistance of 10 ohms
    • 4. Characterization of the inventive low-k dielectric films
  • The low-k dielectric films prepared in accordance with example 3.1 and 3.2 exhibit good transparency and wetting. The low-k dielectric films produced according to example 3.3 have a thickness of 550 nm. After the coating has been calcined, a gold electrode with a layer thickness of 100 to 500 nm is deposited thereon by means of physical vapor deposition. A measurement is then made of the admittance as a function of frequency at room temperature, using a precision LCR meter HP 4284A. At a frequency f of 880 kHz the k value is 2.3.

Claims (7)

  1. A process for producing low-k dielectric film, which comprises using incompletely condensed polyhedral oligomeric silsesquioxanes of structure 1 or 2
    Figure imgb0003
     with
    R = hydrogen atom or alkyl, cycloalkyl, alkenyl, cycloalkenyl,
    alkynyl, cycloalkynyl, aryl or heteroaryl group, in each case substituted or unsubstituted, the substituents R being identical or different as starting material for producing the film.
  2. The process as claimed in claims 1, wherein incompletely condensed polyhedral oligomeric silsesquioxanes are reacted with alkoxysilanes as coreactants capable of hydrolytic condensation.
  3. The process as claimed in claim 2, wherein incompletely condensed polyhedral oligomeric silsesquioxanes are reacted with tetraalkoxysilanes as coreactants capable of hydrolytic condensation.
  4. The process as claimed in at least one of claims 2 to 3, wherein the molar ratio of the incompletely condensed polyhedral oligomeric silsesquioxanes to the coreactant capable of hydrolytic condensation is from 1:10 to 10:1.
  5. The process as claimed in claim 4, wherein the molar ratio of the incompletely condensed polyhedral oligomeric silsesquioxanes to the coreactant capable of hydrolytic condensation is 2:1.
  6. The process as claimed in at least one of claims 1 to 5, wherein the low-k dielectric film is produced by means of a wet-chemical coating method.
  7. The process as claimed in claim 6, wherein the low-k dielectric film is produced by spin coating and subsequent calcining.
EP04741702A 2003-07-03 2004-06-02 Process for producing low-k dielectric films Expired - Lifetime EP1642329B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10330022A DE10330022A1 (en) 2003-07-03 2003-07-03 Process for the preparation of Iow-k dielectric films
PCT/EP2004/050989 WO2005004220A1 (en) 2003-07-03 2004-06-02 Process for producing low-k dielectric films

Publications (2)

Publication Number Publication Date
EP1642329A1 EP1642329A1 (en) 2006-04-05
EP1642329B1 true EP1642329B1 (en) 2011-10-05

Family

ID=33521300

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04741702A Expired - Lifetime EP1642329B1 (en) 2003-07-03 2004-06-02 Process for producing low-k dielectric films

Country Status (9)

Country Link
US (1) US7410914B2 (en)
EP (1) EP1642329B1 (en)
JP (1) JP4518421B2 (en)
KR (1) KR101030244B1 (en)
CN (1) CN100530560C (en)
AT (1) ATE527685T1 (en)
DE (1) DE10330022A1 (en)
ES (1) ES2373721T3 (en)
WO (1) WO2005004220A1 (en)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004114732A1 (en) 2003-06-19 2004-12-29 World Properties, Inc. Material including a liquid crystalline polymer and a polyhedral oligomeric silsesquioxane (poss) filler
DE10357091A1 (en) * 2003-12-06 2005-07-07 Degussa Ag Device and method for the separation of very fine particles from the gas phase
US7549220B2 (en) 2003-12-17 2009-06-23 World Properties, Inc. Method for making a multilayer circuit
GB2427408A (en) * 2004-01-20 2006-12-27 World Properties Inc Circuit Materials Circuits Multi Layer Circuits And Method Of Manufacture
DE102004010055A1 (en) * 2004-03-02 2005-09-22 Degussa Ag Process for the production of silicon
DE102004037675A1 (en) * 2004-08-04 2006-03-16 Degussa Ag Process and apparatus for purifying hydrogen-containing silicon tetrachloride or germanium tetrachloride
CN101180344B (en) * 2005-03-24 2012-01-11 株式会社普利司通 Compounding silica-reinforced rubber with low volatile organic compound (voc) emission
DE102005041137A1 (en) 2005-08-30 2007-03-01 Degussa Ag Plasma reactor for cleaning silicon tetrachloride or germanium tetrachloride, comprises reactor housing, micro unit for plasma treatment, metallic heat exchanger, dielectric, perforated plate, lattice or network and high voltage electrode
DE102006003464A1 (en) * 2006-01-25 2007-07-26 Degussa Gmbh Formation of silicon layer on substrate surface by gas phase deposition, in process for solar cell manufacture, employs silicon tetrachloride as precursor
DE102007007874A1 (en) * 2007-02-14 2008-08-21 Evonik Degussa Gmbh Process for the preparation of higher silanes
DE102007014107A1 (en) 2007-03-21 2008-09-25 Evonik Degussa Gmbh Work-up of boron-containing chlorosilane streams
DE102007048937A1 (en) * 2007-10-12 2009-04-16 Evonik Degussa Gmbh Removal of polar organic compounds and foreign metals from organosilanes
DE102007050199A1 (en) * 2007-10-20 2009-04-23 Evonik Degussa Gmbh Removal of foreign metals from inorganic silanes
DE102007050573A1 (en) * 2007-10-23 2009-04-30 Evonik Degussa Gmbh Large containers for handling and transporting high purity and ultrapure chemicals
DE102007059170A1 (en) * 2007-12-06 2009-06-10 Evonik Degussa Gmbh Catalyst and process for dismutating hydrogen halosilanes
WO2009084562A1 (en) * 2007-12-27 2009-07-09 Nippon Steel Chemical Co., Ltd. Curable silicone copolymer containing cage structure and process for production thereof, and curable resin composition comprising curable silicone copolymer containing cage structure and cured product thereof
DE102008004396A1 (en) * 2008-01-14 2009-07-16 Evonik Degussa Gmbh Plant and method for reducing the content of elements, such as boron, in halosilanes
US8414970B2 (en) * 2008-02-15 2013-04-09 Guardian Industries Corp. Organosiloxane inclusive precursors having ring and/or cage-like structures for use in combustion deposition
DE102008002537A1 (en) * 2008-06-19 2009-12-24 Evonik Degussa Gmbh Process for the removal of boron-containing impurities from halosilanes and plant for carrying out the process
KR101041145B1 (en) * 2008-07-09 2011-06-13 삼성모바일디스플레이주식회사 Polysilsesquioxane copolymer, fabrication method for the same, polysilsesquioxane copolymer thin film using the same, organic light emitting diode display device using the same
DE102008054537A1 (en) * 2008-12-11 2010-06-17 Evonik Degussa Gmbh Removal of foreign metals from silicon compounds by adsorption and / or filtration
US8431670B2 (en) 2009-08-31 2013-04-30 International Business Machines Corporation Photo-patternable dielectric materials and formulations and methods of use
US8623447B2 (en) 2010-12-01 2014-01-07 Xerox Corporation Method for coating dielectric composition for fabricating thin-film transistors
CN109233294B (en) * 2018-08-28 2020-04-24 淮阴工学院 Organic silicon micro-porous ultralow dielectric film and preparation method thereof

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4349609A (en) 1979-06-21 1982-09-14 Fujitsu Limited Electronic device having multilayer wiring structure
US5152834A (en) * 1990-09-14 1992-10-06 Ncr Corporation Spin-on glass composition
US6015457A (en) 1997-04-21 2000-01-18 Alliedsignal Inc. Stable inorganic polymers
US6417115B1 (en) 1998-05-26 2002-07-09 Axeclis Technologies, Inc. Treatment of dielectric materials
US6231989B1 (en) * 1998-11-20 2001-05-15 Dow Corning Corporation Method of forming coatings
US6252030B1 (en) 1999-03-17 2001-06-26 Dow Corning Asia, Ltd. Hydrogenated octasilsesquioxane-vinyl group-containing copolymer and method for manufacture
KR100722731B1 (en) 1999-03-31 2007-05-29 미쓰비시 마테리알 가부시키가이샤 Polyhedral organosilicon compound and method for producing the same
US6440550B1 (en) 1999-10-18 2002-08-27 Honeywell International Inc. Deposition of fluorosilsesquioxane films
JP2001189109A (en) 2000-01-05 2001-07-10 Sumitomo Bakelite Co Ltd Resin composition for insulator, and insulator using the same
TW588072B (en) 2000-10-10 2004-05-21 Shipley Co Llc Antireflective porogens
DE10060775A1 (en) 2000-12-07 2002-06-13 Creavis Tech & Innovation Gmbh Oligomeric silasesquioxanes and process for the preparation of oligomeric silasesquioxanes
DE10060776A1 (en) 2000-12-07 2002-06-13 Creavis Tech & Innovation Gmbh Catalyst system based on polymer compounds containing silase sequioxane-metal complexes
DE10100384A1 (en) 2001-01-05 2002-07-11 Degussa Process for modifying the functionality of organofunctional substrate surfaces
US6936537B2 (en) * 2001-06-19 2005-08-30 The Boc Group, Inc. Methods for forming low-k dielectric films
WO2003064490A2 (en) * 2001-06-27 2003-08-07 Hybrid Plastics Llp Process for the functionalization of polyhedral oligomeric silsesquioxanes
DE10141687A1 (en) 2001-08-25 2003-03-06 Degussa Agent for coating surfaces containing silicon compounds
WO2003024870A1 (en) * 2001-09-18 2003-03-27 Chisso Corporation Silsesquioxane derivatives and process for production thereof
DE10156619A1 (en) 2001-11-17 2003-05-28 Creavis Tech & Innovation Gmbh Process for the preparation of functionalized oligomeric silasesquioxanes and their use

Also Published As

Publication number Publication date
CN100530560C (en) 2009-08-19
KR101030244B1 (en) 2011-04-25
ES2373721T3 (en) 2012-02-08
DE10330022A1 (en) 2005-01-20
ATE527685T1 (en) 2011-10-15
US20070166456A1 (en) 2007-07-19
KR20060031678A (en) 2006-04-12
EP1642329A1 (en) 2006-04-05
US7410914B2 (en) 2008-08-12
JP4518421B2 (en) 2010-08-04
WO2005004220A1 (en) 2005-01-13
JP2009514189A (en) 2009-04-02
CN1816902A (en) 2006-08-09

Similar Documents

Publication Publication Date Title
EP1642329B1 (en) Process for producing low-k dielectric films
KR100802349B1 (en) Porous siliceous film having low permittivity, process for the preparation thereof and semiconductor devices comprising the same
US7238627B2 (en) Organosilicate polymer and insulating film therefrom
JP2003501518A (en) Low dielectric constant polyorganosilicon coating derived from polycarbosilane
JP2003007699A (en) Low-permittivity material and processing method according to cvd
KR100727277B1 (en) Low-permittivity porous siliceous film and semiconductor devices having such films
JP3919862B2 (en) Method for forming low dielectric constant siliceous film and siliceous film
JP3939408B2 (en) Low dielectric constant siliceous film
WO2004044972A1 (en) Composition for porous film formation, porous films, process for production of the films, interlayer dielectrics, and semiconductor devices
US7090896B2 (en) Process for producing dielectric layers by using multifunctional carbosilanes
JP2002201415A (en) Application liquid for silica-based coating film formation, method for manufacturing silica-based coating film, and semiconductor device
KR20220074611A (en) Fluorine-based organopolysilazane and method for manufacturing the same
JPH05214296A (en) Coating fluid for forming oxide film and formation of oxide film
JP4053105B2 (en) Method for forming siliceous ceramic coating and ceramic coating formed by the same method
KR100422916B1 (en) Organic silicate polymer and low dielectric insulation film comprising the same
JPH07173434A (en) Coating fluid for forming oxide film and production of oxide film
JP3881420B2 (en) Low dielectric constant material, interlayer insulation film and IC substrate
JPH06136124A (en) Production of coating soluton for forming silica film, production of silica film, silica film, and semiconductor device
JPH0995646A (en) Coating composition for silica-based coating film and base material with silica-based coating film
KR100508902B1 (en) Organic silicate polymer and insulation film comprising the same
JP2000212508A (en) Coating liquid for forming silica-based coating film, production of silica-based coating film, silica-based coating film and semiconductor device produced by using the liquid
KR20050050032A (en) Siloxane-based resin using molecular polyhedral silsesquioxane and method for forming dielectric film using the same
JPH1112540A (en) Coating liquid for forming silica-based coating film, silica-based coating film and semiconductor device using the same
JP2006028473A (en) Organic/inorganic composite, its manufacturing method, and semiconductor device using the same
JP2006324352A (en) Organic inorganic matter complex, manufacturing method thereof, and semiconductor device

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20051208

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: DEGUSSA GMBH

RIN1 Information on inventor provided before grant (corrected)

Inventor name: RAULEDER, HARTWIG

Inventor name: KUEHNLE, ADOLF

Inventor name: VAN DAM, ROELANT

Inventor name: FISCHER, HARTMUT

Inventor name: TIMMER, KLAAS

Inventor name: RENTROP, CORNE

Inventor name: JOST, CARSTEN

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: EVONIK DEGUSSA GMBH

17Q First examination report despatched

Effective date: 20090525

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602004034682

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: H01L0021312000

Ipc: H01L0021316000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: C09D 183/04 20060101ALI20110518BHEP

Ipc: H01L 21/316 20060101AFI20110518BHEP

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602004034682

Country of ref document: DE

Effective date: 20111201

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20111005

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2373721

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20120208

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 527685

Country of ref document: AT

Kind code of ref document: T

Effective date: 20111005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120206

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20120105

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20120622

Year of fee payment: 9

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120705

Year of fee payment: 9

26N No opposition filed

Effective date: 20120706

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120626

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20120621

Year of fee payment: 9

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004034682

Country of ref document: DE

Effective date: 20120706

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20120627

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20120602

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120602

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

BERE Be: lapsed

Owner name: EVONIK DEGUSSA G.M.B.H.

Effective date: 20130630

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602004034682

Country of ref document: DE

Effective date: 20140101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140101

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20111005

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120602

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040602

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20150709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130603